CN115232636B - Method and apparatus for determining a Fischer-Tropsch catalyst replacement strategy in a run-time reactor - Google Patents
Method and apparatus for determining a Fischer-Tropsch catalyst replacement strategy in a run-time reactor Download PDFInfo
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- C10G2/34—Apparatus, reactors
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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Abstract
The invention provides a method and a device for determining a Fischer-Tropsch catalyst replacement strategy in a reactor during operation, and belongs to the technical field of Fischer-Tropsch synthesis. The method comprises the following steps: acquiring an initial catalyst replacement interval and an initial catalyst replacement proportion; determining a catalyst ratio corresponding to the operating time based on a pre-established catalyst ratio distribution model, an initial catalyst replacement interval and an initial catalyst replacement ratio; determining the catalyst activity corresponding to the operation time based on a pre-established catalyst deactivation model; determining a catalyst integrated activity corresponding to the run length based on the catalyst activity, the catalyst proportion, the initial catalyst replacement interval, and the initial catalyst replacement proportion; determining a loss ratio based on a pre-established loss model and the comprehensive activity of the catalyst; and adjusting the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio to determine the replacement interval and the replacement ratio for replacing the Fischer-Tropsch catalyst in the reactor. Thus, a suitable replacement strategy can be obtained.
Description
Technical Field
The invention relates to the technical field of Fischer-Tropsch synthesis, in particular to a method and a device for determining a Fischer-Tropsch catalyst replacement strategy in a reactor during operation.
Background
Based on the characteristics of rich coal, lean oil and low-gas energy structures in China and the increasingly severe environmental protection performance requirements of oil products, the great development of the indirect coal liquefaction technology taking Fischer-Tropsch synthesis as a core has important significance. Compared with the traditional petroleum refining process, the product of indirect coal liquefaction is cleaner, and the product scheme is more flexible. Meanwhile, the development of indirect coal liquefaction has certain economic advantages in the face of the complex situations of international situation and unstable crude oil price, and is also a strategic reserve.
The Fischer-Tropsch synthesis process realizes conversion of synthesis gas to hydrocarbon under the action of a solid catalyst. In the production process of the coal indirect liquefaction project, the core Fischer-Tropsch synthesis process needs to maintain excellent and stable production performance, and the catalyst in the Fischer-Tropsch synthesis reactor is easy to be deactivated due to factors such as oxidation, carbon deposition, sintering, abrasion and the like in the reaction process of the catalyst in the reactor. Therefore, in industrial operation, in order to ensure the stability of the catalytic performance, it is necessary to periodically replace the catalyst in the reactor, i.e. to discharge a portion of the old catalyst in the reactor and to replenish the newly reduced and activated catalyst with a corresponding mass. In industrial production, the replacement operation needs to be performed on-line, and it is required that the production process cannot be greatly affected.
Theoretically, in order to maintain the activity and productivity of the catalyst in the reactor at a high level, the larger the amount of the catalyst to be replaced, the better the shorter the interval of the replacement. However, such an operation causes a large loss of the catalyst, which results in a problem of high catalyst consumption, low utilization rate and high cost.
For example, patent application number CN201710982743.7 discloses an online feeding method of catalyst in slurry bed reactor and a special equipment system thereof, which can realize stable, uniform and accurate quantitative catalyst feeding to slurry bed reactor. The feeding method is characterized in that metering is carried out before Fischer-Tropsch catalyst reduction, catalyst activation is carried out in a slurry bed reduction mode, and the catalyst is conveyed into a Fischer-Tropsch synthesis reactor by means of hydraulic force, so that the method has the advantages of wide feeding amount application range and accurate numerical value.
Patent application number CN201510695526.0 discloses a slurry bed reactor catalyst replacement system and method. The replacement method adopts a replacement method combining periodic replacement of the catalyst and massive replacement of the catalyst. The method provides that the interval of periodically replacing the catalyst is 5 days, the replacement amount is 4.5 tons, and the large amount of the catalyst is replaced by adding the catalyst which is reduced twice continuously into the slurry bed reactor once a month, so that the large amount of the catalyst is replaced.
Patent application number CN201810494652.3 discloses an online catalyst updating device and method for slurry bed fischer-tropsch synthesis reactor. The method employs a fluidized bed reactor to activate the Fischer-Tropsch catalyst, and the catalyst is stored in a storage tank and transferred to a slurry bed Fischer-Tropsch synthesis reactor at an appropriate time. The method can be used for replacing and updating the catalyst of the Fischer-Tropsch synthesis reactor in a short period and small proportion after a large amount of activated catalyst.
The above patent describes a method and apparatus for the periodic replacement of the catalyst within a fischer-tropsch synthesis reactor. Wherein the Fischer-Tropsch synthesis reactor is a slurry bed, and the reduction reactor with a new catalyst source comprises a slurry bed and a fluidized bed. The method provided by the patent can confirm that the Fischer-Tropsch catalyst can be replaced on line in the Fischer-Tropsch synthesis production process, and specific values of the discharge and addition amount can be determined. Among the above schemes, some schemes directly give the substitution interval and the substitution amount, and some schemes are not clear. The above-described schemes do not disclose or teach how the displacement interval and displacement amount are determined and thus can only be adapted to a specific range of production situations.
Disclosure of Invention
It is an aim of embodiments of the present invention to provide a method and apparatus for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor, which addresses one or more of the above-mentioned technical problems.
To achieve the above object, embodiments of the present invention provide a method for determining a fischer-tropsch catalyst replacement strategy in a reactor during operation, the fischer-tropsch catalyst replacement strategy comprising a replacement interval and a replacement ratio for replacing a fischer-tropsch catalyst in the reactor, the method comprising: acquiring an initial catalyst replacement interval and an initial catalyst replacement proportion; determining a catalyst ratio corresponding to an operating duration based on a pre-established catalyst ratio distribution model, the initial catalyst replacement interval, and the initial catalyst replacement ratio; determining the catalyst activity corresponding to the operation time based on a pre-established catalyst deactivation model; determining a catalyst integrated activity corresponding to the operating duration based on the catalyst activity, the catalyst proportion, the initial catalyst replacement interval, and the initial catalyst replacement proportion; determining a loss ratio based on a pre-established loss model and the catalyst integrated activity; and adjusting the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio to determine the replacement interval and the replacement ratio for replacing the Fischer-Tropsch catalyst in the reactor.
Optionally, the adjusting the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio includes: obtaining a catalyst replacement interval limit value and a catalyst replacement proportion limit value; selecting an adjusted catalyst replacement interval from a range of catalyst replacement intervals consisting of the catalyst replacement interval limit and the initial catalyst replacement interval; and selecting an adjusted catalyst replacement ratio from a range of catalyst replacement ratios consisting of the catalyst replacement ratio limit and the initial catalyst replacement ratio.
Optionally, the catalyst ratio distribution model is established by the following formula: t-τ h ；k·(1-k) n-i T-T- (i-1) & Δt, wherein m 0 And m h The mass of the catalyst is added in the start-up stage, h is the additive number in the start-up stage, M is the catalyst inventory, k is the replacement proportion, n is the total number of replacement, i is the replacement number, τ h To add in the start-up stageThe time interval for entering the catalyst, T is the operation duration, T is the time for entering the stable displacement phase, and Δt is the catalyst displacement interval.
Optionally, the catalyst activity comprises one or more of: conversion of CO, CO 2 Selectivity, CH 4 Selectivity and c3+ selectivity.
Optionally, the method further comprises determining the catalyst integrated activity corresponding to the operating time period by the following formula:
Wherein y represents the comprehensive activity of the catalyst, m 0 And m h The mass of the catalyst is added in the start-up stage, p is the total number of times of the catalyst in the start-up stage, h is the number of times of the catalyst in the start-up stage, M is the catalyst inventory, k is the replacement proportion, n is the total number of times of replacement, i is the replacement number, τ h The time interval for adding the catalyst in the start-up stage is T the operation time, T the time for entering the stable replacement stage, deltat the catalyst replacement interval, and g (T) the catalyst activity.
Optionally, the loss model is established by:
where n is the total number of permutations.
Optionally, the initial catalyst replacement interval and the initial catalyst replacement ratio are determined by a reduction time of a predetermined amount of catalyst, wherein the initial catalyst replacement interval is the reduction time of the predetermined amount of catalyst; and the initial catalyst replacement ratio is the ratio of the predetermined amount of catalyst to the total catalyst.
Accordingly, an embodiment of the present invention also provides an apparatus for determining a fischer-tropsch catalyst replacement strategy in a reactor during operation, the fischer-tropsch catalyst replacement strategy comprising a replacement interval and a replacement ratio for replacing a fischer-tropsch catalyst in the reactor, the apparatus comprising: the acquisition module is used for acquiring an initial catalyst replacement interval and an initial catalyst replacement proportion; the determining module is used for executing the following operations: determining a catalyst ratio corresponding to the run length based on a pre-established catalyst ratio distribution model, the initial catalyst replacement interval, and the initial catalyst replacement ratio; determining the catalyst activity corresponding to the operation time based on a pre-established catalyst deactivation model; determining a catalyst integrated activity corresponding to the operating duration based on the catalyst activity, the catalyst proportion, the initial catalyst replacement interval, and the initial catalyst replacement proportion; determining a loss ratio based on a pre-established loss model and the comprehensive activity of the catalyst; and the adjusting module is used for adjusting the catalyst replacement interval and the catalyst replacement proportion according to the loss ratio so as to determine the replacement interval and the replacement proportion for replacing the Fischer-Tropsch catalyst in the reactor.
In another aspect, the application provides a machine-readable storage medium having stored thereon instructions for causing a machine to perform a method for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor according to any of the preceding claims.
In another aspect, the application provides a processor for running a program which when run is adapted to perform the method for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor as defined in any one of the preceding claims.
Through the technical scheme, a user can adjust the catalyst replacement proportion and the catalyst replacement interval to the values which are most in line with the user's expectations according to the actual demands. The technical scheme can also solve the problem of how to quantitatively confirm the catalyst replacement interval and the catalyst replacement proportion based on the data, and effectively improve the scientificity and the high efficiency of production decisions.
Additional features and advantages of embodiments of the application will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain, without limitation, the embodiments of the application. In the drawings:
FIG. 1 is a schematic diagram of a catalyst replacement scheme in a Fischer-Tropsch synthesis reaction process according to an embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a method for determining a Fischer-Tropsch catalyst replacement strategy in a run-time reactor provided by an embodiment of the invention;
FIG. 3 is a schematic flow diagram of a method for determining a Fischer-Tropsch catalyst replacement strategy in a run-time reactor provided by an embodiment of the invention;
FIG. 4 is a block diagram of an apparatus for determining a Fischer-Tropsch catalyst replacement strategy in a run-time reactor, according to an embodiment of the invention.
Description of the reference numerals
1. Catalyst reduction activation reactor 2 Fischer-Tropsch synthesis reactor
3. New reduction activation catalyst in slag wax collecting tank 4
5. Fresh synthesis gas from old catalyst 6
7. Module is acquireed to oil and tail gas 410
420. Determination module 430 adjustment module
Detailed Description
The following describes the detailed implementation of the embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
To facilitate an understanding of the Fischer-Tropsch reactor catalyst replacement process, an explanation will now be made in connection with the Fischer-Tropsch reactor catalyst replacement flow scheme shown in FIG. 1.
As shown in fig. 1, a catalyst is placed in a catalyst reduction activation reactor 1, wherein a new reduction activation catalyst 4 and fresh synthesis gas 6 are sent to a fischer-tropsch synthesis reactor 2 to participate in the fischer-tropsch synthesis reaction, oil products and tail gases 7 generated after the reaction are discharged from the fischer-tropsch synthesis reactor 2 and collected, and meanwhile, an old catalyst 5 is discharged from the fischer-tropsch synthesis reactor 2 to a paraffin collection tank 3 and collected. The scheme completes the replacement of the catalyst through the discharge of the old catalyst and the injection of the new reduction activation catalyst, so that the production process can be maintained in a stable production state.
Based on the catalyst replacement flow of the fischer-tropsch synthesis reactor provided in the above embodiments, the present application provides a method for determining a fischer-tropsch catalyst replacement strategy in the reactor during operation, which can help a worker determine a suitable catalyst replacement interval and catalyst replacement ratio, so as to achieve the following optimization effects: the practicality of catalyst replacement and the production efficiency are improved while the production stability is ensured. Among them, in the stable production process, it is necessary to keep the catalyst inventory in the reactor in a substantially stable state, and therefore, for convenience of description, it is proposed in the present application to describe the displacement amount information of the catalyst by the displacement ratio.
FIG. 2 is a schematic flow diagram of a method for determining a Fischer-Tropsch catalyst replacement strategy in a run-time reactor, provided in an embodiment of the invention. As shown in fig. 2, the method for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor comprises steps S1210 to S260.
In step S210, an initial catalyst replacement interval and an initial catalyst replacement ratio are acquired.
The manner of determining the obtained initial catalyst replacement interval and initial catalyst replacement ratio may be selected from the following manners: the initial catalyst replacement interval and the initial catalyst replacement ratio are selected from historical production parameters, the initial catalyst replacement interval and the initial catalyst replacement ratio are selected based on accumulated production experience or worker experience, or the initial catalyst replacement interval and the initial catalyst replacement ratio are selected from relevant parameters simulating Fischer-Tropsch synthesis reaction, and the like.
In order to be able to evaluate the exact and reliable operating time, the time period consumed for reducing a batch of catalyst is preferably used as the initial displacement interval.
For example, the initial catalyst replacement interval is the reduction time of a predetermined amount of catalyst, and the initial catalyst replacement ratio is the ratio of the predetermined amount of catalyst to the total catalyst.
Wherein the predetermined amount of the maximum catalyst is based on the maximum reduction amount of the catalyst reduction activation reactor.
Wherein, the initial catalyst replacement interval can be further considered to be time-consuming in consideration of the process based on the reduction time of the predetermined amount of catalyst so as to have a sufficient catalyst replacement preparation time.
In step S220, a catalyst ratio corresponding to the operation duration is determined based on the pre-established catalyst ratio distribution model, the initial catalyst replacement interval, and the initial catalyst replacement ratio.
The pre-established catalyst proportion distribution model is mainly used for determining the catalyst proportion distribution condition in the Fischer-Tropsch synthesis reactor when the Fischer-Tropsch synthesis reaction is operated to different operation time lengths.
Considering that the Fischer-Tropsch synthesis reactor for industrial production runs for a long period and can be divided into a start-up stage and a stable operation stage, the embodiment of the invention also provides a method for establishing a catalyst proportion distribution model aiming at the characteristics of catalyst replacement in the two working stages.
In the start-up stage, a certain mass of catalyst needs to be transferred to the Fischer-Tropsch synthesis reactor in batches according to the activation capacity of the catalyst reduction activation reactor until the catalyst inventory meets the requirement. During this process, a certain amount of catalyst may be replaced according to the operation conditions, but the replacement ratio and the replacement interval are unstable, and the start-up period is usually less than 500 hours.
Thus, the catalyst ratio distribution model at start-up stage is built by the following formula:the operation time is t; />The operation time is t-tau h . Wherein m is 0 And m h The mass of the catalyst is added in the start-up stage, h is the number of the catalyst in the start-up stage, M is the catalyst inventory, k is the replacement proportion, n is the total number of replacement times, and tau h The time interval for adding the catalyst for the start-up stage is t the operating time.
Wherein, h has the values of 1,2,3, … … and p. Correspondingly, m 1 To m p Indicating the mass of catalyst added in different batches during the start-up phase, τ 1 To tau p The time intervals for the addition of catalyst to the different batches during the start-up phase are indicated.
After the catalyst inventory is met and the system is stable, a stable displacement phase is entered. In the stable operation stage, the Fischer-Tropsch synthesis reactor needs to regularly discharge a certain proportion of used catalyst and supplement new catalyst with the same mass so as to ensure stable catalyst inventory and stable production efficiency.
Thus, the catalyst ratio distribution model for the steady operation phase is established by the following formula: k (1-k) n-i The operation time is T-T- (i-1). DELTA.t. Wherein k is the replacement proportion, n is the total number of times of replacement, i is the replacement sequence number, T is the operation duration, T is the time for entering the stable replacement stage, deltat is the catalyst replacement interval, and i has the values of 1,2,3, … … and n.
Wherein, when a pre-established catalyst proportion distribution model is preliminarily used, the replacement proportion k and the catalyst replacement interval delta t in the model are respectively the obtained initial catalyst replacement proportion k 0 And an initial catalyst replacement interval Δt 0 。
In addition, based on the length of the run, the time to enter the stable metathesis stage, and the catalyst metathesis interval, the total number of metathesis n can be determined based on the following equation:
in step S230, the catalyst activity corresponding to the operation duration is determined based on a pre-established catalyst deactivation model.
Based on catalysts employed in Fischer-Tropsch synthesisThe types of catalyst activities involved may include one or more of the following: conversion of CO, CO 2 Selectivity, CH 4 Selectivity and c3+ selectivity.
The catalyst deactivation model involved in this step may be a general model based on data or a theoretical model based on a mechanism, as long as the catalyst activity corresponding to time can be determined based on the catalyst deactivation model.
For example, a general model based on data may be selected as the catalyst deactivation model. The data can be obtained through a catalyst non-replacement long-period evaluation test of a corresponding small-scale device, the dependent variable of the model is the relative activity of the catalyst (namely the ratio of the activity of the catalyst to the initial activity of the catalyst at a certain moment), and the independent variable of the model is the natural logarithm of time. Wherein the catalyst should not be displaced for a long period of time longer than 1000 hours, preferably longer than 2000 hours.
A method of modeling catalyst deactivation based on pilot experimental data will now be explained. The duration of the pilot run batch of catalyst without replacement for the long period was 2000 hours. In the method, the fitted catalyst deactivation model is a 6-segment Gaussian mixture model, and the fitting goodness R of the model is verified by multiple experimental data 2 All are more than 97 percent.
Specifically, a catalyst deactivation model constructed from a 6-segment gaussian mixture model is shown below:where f (x) represents catalyst activity, a, b and c are parameters (depending on pilot experimental data), e is the natural logarithm, x is time dependent (e.g. x is lnt, t is the run length).
In step S240, the catalyst integrated activity corresponding to the operation duration is determined based on the catalyst activity, the catalyst ratio, the initial catalyst replacement interval, and the initial catalyst replacement ratio.
This embodiment of the present invention provides a method for determining the catalyst integrated activity corresponding to the operation duration by combining the pre-established catalyst proportion distribution model and the pre-established catalyst deactivation model provided in the above embodiment of the present invention, and the catalyst integrated activity may be specifically determined by the following formula:
wherein y represents the comprehensive activity of the catalyst, m 0 And m h The mass of the catalyst is added in the start-up stage, p is the total number of times of the catalyst in the start-up stage, h is the number of times of the catalyst in the start-up stage, M is the catalyst inventory, k is the replacement proportion, n is the total number of times of replacement, i is the replacement number, τ h The time interval for adding the catalyst in the start-up stage is T the operation time, T the time for entering the stable replacement stage, deltat the catalyst replacement interval, and g (T) the catalyst activity.
Wherein the substitution ratio k and the catalyst substitution interval Δt in the formula for determining the catalyst integrated activity are the same as the substitution ratio k and the catalyst substitution interval Δt in the catalyst ratio distribution model corresponding to the catalyst ratio distribution model. For example, in the preliminary use, the substitution ratio k and the catalyst substitution interval Δt in the formula for determining the overall catalyst activity are respectively the initial catalyst substitution ratio k obtained 0 And an initial catalyst replacement interval Δt 0 。
Wherein, for the catalyst comprehensive activity y, y is E (XCO, YCO) 2 ,YCH 4 Yc3+, etc.), X represents conversion, and Y represents selectivity.
Wherein, in the case of selecting the catalyst deactivation model f (x) constructed by the 6-stage gaussian mixture model provided in the above embodiment in step S130, g (t) =f (lnt) ·initial activity value.
The catalyst composite activity referred to in this example of the invention can exhibit composite activity of the catalyst at different operating time points under different catalyst replacement conditions.
In step S250, the attrition ratio is determined based on a pre-established attrition model and catalyst composite activity.
The loss ratio is used primarily to characterize the effect of the replacement catalyst on production. On the basis, the embodiment of the invention provides a method for establishing a loss model, which is used for the loss ratio corresponding to the catalyst replacement interval and the catalyst replacement proportion.
For industrial production, performance indexes such as oil production, oil-gas ton consumption and oil-agent ton consumption are involved, so that the performance indexes at different moments can be calculated in an accumulated manner to obtain total oil production, total gas consumption, total agent consumption and the like. Based on the calculation results, a relationship between comprehensively considering the total oil production, gas consumption, agent consumption and replacement operation cost in the operation duration range can be established.
Specifically, the loss model may be built up to determine the loss ratio by the following formula:
where n is the total number of permutations.
The loss model established based on the method provided by the embodiment of the invention can determine the loss cost in the production process based on the current market conditions, so that an effective and reasonable adjustment direction can be provided for the subsequent catalyst replacement proportion and catalyst replacement interval.
In step S260, the catalyst replacement interval and the catalyst replacement ratio are adjusted according to the attrition ratio to determine the replacement interval and the replacement ratio for replacing the fischer-tropsch catalyst in the reactor.
For adjusting the catalyst replacement interval and the catalyst replacement ratio, an appropriate adjustment mode and adjustment trend can be selected by self based on the actual production plan.
For example, the catalyst replacement interval limit and the catalyst replacement ratio limit may be set first, and then the adjusted catalyst replacement interval may be selected from the catalyst replacement interval range consisting of the catalyst replacement interval limit and the initial catalyst replacement interval, and/or the adjusted catalyst replacement ratio may be selected from the catalyst replacement ratio range consisting of the catalyst replacement ratio limit and the initial catalyst replacement ratio.
Wherein the catalyst replacement interval limit is dependent on the processing time of the catalyst reduction process and the catalyst replacement ratio limit is dependent on the catalyst inventory and the throughput of the catalyst reduction process.
On the basis of the determination of the catalyst replacement interval limit and the catalyst replacement ratio limit, the catalyst replacement interval and the catalyst replacement ratio may be adjusted in a certain direction and in a certain constraint range, and the above steps S210 to S250 are repeated.
After repeating steps S210 to S250 a plurality of times, a plurality of groups of replacement parameters including a catalyst replacement interval and a catalyst replacement ratio and a loss ratio corresponding thereto can be obtained. Therefore, reasonable value basis can be provided for the selection of the catalyst replacement interval and the catalyst replacement proportion in the Fischer-Tropsch synthesis reaction.
For example, the catalyst replacement interval and the catalyst replacement ratio corresponding to the lowest value of the loss ratio may be selected as the optimal selection, or a plurality of sets of the catalyst replacement interval and the catalyst replacement ratio may be selected as the candidate parameters. Specifically, the catalyst replacement interval and the corresponding catalyst replacement ratio with the loss ratio within a certain range can be used as alternative parameters, so that when different production capacities and production requirements exist, the catalyst replacement interval and the catalyst replacement ratio can be selected and used as a replacement strategy of the Fischer-Tropsch catalyst in the reactor during operation, and the Fischer-Tropsch catalyst in the reactor during operation can be replaced.
According to the method for determining the Fischer-Tropsch catalyst replacement strategy in the reactor during operation, provided by the embodiment of the invention, a user can adjust the catalyst replacement proportion and the catalyst replacement interval to the values which are most in line with the user expectations according to actual requirements. The method can solve the problem of how to quantitatively confirm the catalyst replacement interval and the catalyst replacement proportion based on data in the industrial production process, and effectively improves the scientificity and the high efficiency of production decisions.
The method for determining the Fischer-Tropsch catalyst replacement strategy in the reactor during operation provided by the embodiment of the invention provides operability for a user to adjust the parameters of the catalyst deactivation model according to the catalyst type number, and can also assist the user to obtain proper catalyst replacement intervals and catalyst replacement proportions according to the dynamic market state, so that the scheme has strong practicability and can adapt to the market state.
The embodiment of the invention also provides a method for determining the Fischer-Tropsch catalyst replacement strategy in the reactor during operation, and the specific process is shown in figure 3.
In step S301, the following values are determined: catalyst replacement interval Δt 0 Catalyst replacement ratio k 0 And the operation time t, the number of times of the primary cycle is recorded as j=0, and r=0.
In step S302, the number of permutations is calculated, the catalyst proportion distribution corresponding to each hour in the operation time period t is calculated based on the catalyst proportion distribution models of different operation time periods, and the catalyst activity corresponding to each hour is determined based on the catalyst deactivation model.
In step S303, the catalyst integrated activity for each hour is determined based on the corresponding catalyst proportion distribution and the corresponding catalyst activity for each hour, and the corresponding output value and loss value for each hour are calculated at the same time.
In step S304, the total output value and the loss value in the operation time period t are determined based on the performance index, and the total loss ratio is determined.
In step S305, a total loss duty ratio P is based jr Corresponding catalyst replacement ratio k j And catalyst replacement interval Δt r 。
In step S306, j=j+1, k j ＝k 0 +1。
In step S307, determine k j Whether or not it is greater thanIf yes, go to step S308, otherwise go to step S302.
In step S380, r=r+1, Δt r ＝Δt 0 +1。
In step S309, Δt is determined r Whether or not it is greater than the upper limit value deltat Upper limit of If yes, go to step S310, otherwise go to step S302.
In step S310, the smallest P is confirmed jr And return the corresponding delta t r And k j 。
Shown in the current step S310 is a set of permutation intervals and permutation ratios, which correspond to minimum loss duty cycles.
On the basis of this, the improvement can be performed in step S310, that is, one or more groups of the replacement intervals and the replacement ratios with the loss ratio within the preset range are all output and stored in the record.
The scheme provided by the embodiment of the invention can solve the problem of how to determine the catalyst replacement interval and the replacement proportion in industrial production, so as to improve the scientificity and the high efficiency of production decisions.
The scheme provided by the embodiment of the invention is explained in detail in connection with the stable displacement stage of a slurry bed reactor of an industrial scale for a certain industrial application of a fischer-tropsch catalyst.
Step 1: determination of initial value Δt of catalyst replacement interval and ratio 0 72h, k 0 5% and the investigation run time t is 5000h.
Step 2: the catalyst ratio distribution of different retention time periods in the reactor was calculated.
The method specifically comprises the following steps: (1) confirming the dosing condition of the starting stage; (2) confirming the stable replacement starting time; (3) calculating the total number of replacement times; (4) the catalyst ratios for the different retention periods were calculated.
Step 3: and (3) establishing a catalyst deactivation model, and calculating the catalyst activity corresponding to different retention time lengths.
The method specifically comprises the following steps: (1) establishing a catalyst deactivation model according to pilot experiment data, wherein the evaluation time of the pilot experiment is 2000 hours, the fitted catalyst deactivation model is a 6-segment Gaussian mixture model, and the fitting goodness R is obtained 2 All greater than 97%; (2) the initial value of the activity of the catalyst under given industrial conditions; (3) and calculating the catalyst activity corresponding to different retention time periods.
Step 4: and calculating the comprehensive performance of the catalyst in the reactor at different moments within 5000 hours of operation time.
Step 5: and calculating the industrial performance indexes of the catalyst at different moments within 5000 hours of the operation duration.
The method specifically comprises the following steps: (1) given parameters such as fresh synthetic gas inflow, effective gas proportion, H2/CO and the like, (2) calculating performance indexes such as oil yield, oil and gas consumption per ton, oil and agent consumption per ton and the like.
Step 6: and performing cumulative calculation on performance indexes at different moments in the operation time to obtain total oil production, total gas consumption, total agent consumption and the like, establishing a loss model comprehensively considering the total oil production, gas consumption, agent consumption and replacement operation cost in the operation time range, and calculating the loss ratio.
The method specifically comprises the following steps: (1) performing cumulative calculation on performance indexes at different moments to obtain total oil yield, total gas consumption, total agent consumption and the like; (2) obtaining the production cost such as oil selling price, synthesis gas cost, catalyst cost, reduction operation cost, catalyst replacement cost and the like; (3) the loss duty cycle is calculated.
Step 7: and (3) increasing the values of the replacement interval and the replacement proportion, and repeating the steps 2 to 6 to obtain the conditions of different conditions until the constraint limit value is reached.
The method specifically comprises the following steps: (1) confirming the limit value of the constraint condition, wherein the replacement proportion is less than or equal to 11%, and the upper limit of the replacement interval is 144h; (2) the loss duty cycle for the different substitution conditions is calculated.
Step 8: based on the loss ratio, an optimal substitution interval of 84h and an optimal substitution ratio of 11% are determined.
Based on the above embodiments, the simulation, original industrial actual conditions and the optimized industrial actual conditions of the performance index under the conditions of the optimal displacement interval and the optimal displacement ratio are shown in table 1.
As can be seen from the comparison of the table 1, the simulation value obtained by the method provided by the invention is very close to the industrial actual value under the same condition, the reliability of the adjusted optimal replacement interval and the optimal replacement proportion obtained by the method is high, and meanwhile, compared with the original industrial result, the industrial stable operation result according to the optimal replacement condition has lower oil-gas consumption per ton and higher oil-gas consumption per ton, but the production benefit is better.
FIG. 4 is a block diagram of an apparatus for determining a Fischer-Tropsch catalyst replacement strategy in a run-time reactor, according to an embodiment of the invention. As shown in fig. 4, the apparatus for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor comprises an acquisition module 410, a determination module 420 and an adjustment module 430. Wherein the obtaining module 410 is configured to obtain an initial catalyst replacement interval and an initial catalyst replacement ratio; the determining module 420 is configured to determine a catalyst ratio corresponding to the operation duration based on a pre-established catalyst ratio distribution model, the initial catalyst replacement interval, and the initial catalyst replacement ratio, determine a catalyst activity corresponding to the operation duration based on a pre-established catalyst deactivation model, determine a catalyst comprehensive activity corresponding to the operation duration based on the catalyst activity, the catalyst ratio, the initial catalyst replacement interval, and the initial catalyst replacement ratio, and determine a loss duty based on a pre-established loss model and the catalyst comprehensive activity; the adjustment module 430 is configured to adjust the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio, so as to determine the replacement interval and the replacement ratio for adjusting the fischer-tropsch catalyst, and use the replacement interval and the replacement ratio for adjusting the fischer-tropsch catalyst as a replacement strategy of the fischer-tropsch catalyst in the reactor during operation.
The acquisition module is used for acquiring the initial catalyst replacement interval and the initial catalyst replacement proportion, and acquiring parameter values, coefficients and the like for constructing the model. For example, the acquisition module may also acquire oil sales prices, syngas cost prices, catalyst cost prices, cost per replacement operation prices, fresh syngas intake, effective gas proportions, fresh syngas H 2 CO, initial catalyst activity and/or deactivation model parameters for industrial operations, etc.
Based on various models established in advance, the determining module can determine various data in the operation time in the process of executing corresponding operations, for example, the comprehensive activity of the mixed catalyst at different moments can be determined based on the catalyst proportion distribution condition of different operation time and the corresponding catalyst activity based on the catalyst deactivation model, and then the comprehensive activity of the catalyst is utilized to determine the production performance index, such as oil yield, oil-gas ton consumption and the like, of each time point of each time period. The cumulative value is then calculated based on the production performance index at each time point within the operating time period, so that the loss ratio can be determined based on the loss model.
In the process of adjusting the catalyst replacement interval and the catalyst replacement ratio by the adjustment module, the catalyst replacement interval and the catalyst replacement ratio also need to be controlled within a constraint range.
In addition, based on the user requirement, the adjustment module can return the optimal group data or can return all the group data meeting the conditions so as to be convenient for the user to take.
With respect to the specific details and benefits of the apparatus for determining a fischer-tropsch catalyst replacement strategy in a runtime reactor provided by the above embodiments of the present invention, reference may be made to the specific details and benefits of the method for determining a fischer-tropsch catalyst replacement strategy in a runtime reactor provided by the present invention, which are not described in detail herein.
The device for determining the Fischer-Tropsch catalyst replacement strategy in the reactor during operation comprises a processor and a memory, wherein the acquisition module, the determination module, the adjustment module and the like are all stored in the memory as program units, and the processor executes the program units stored in the memory to realize corresponding functions.
The processor includes a kernel, and the kernel fetches the corresponding program unit from the memory. The core can be provided with one or more than one core, and the proper replacement interval and replacement proportion of the Fischer-Tropsch catalyst are obtained according to the loss ratio by adjusting the parameters of the core.
The memory may include volatile memory, random Access Memory (RAM), and/or nonvolatile memory, such as Read Only Memory (ROM) or flash memory (flash RAM), among other forms in computer readable media, the memory including at least one memory chip.
Embodiments of the present application provide a storage medium having a program stored thereon, which when executed by a processor, implements the method for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor.
The embodiment of the application provides a processor which is used for running a program, wherein the program runs to execute the method for determining the Fischer-Tropsch catalyst replacement strategy in a reactor during running.
The embodiment of the application provides equipment, which comprises a processor, a memory and a program stored in the memory and capable of running on the processor, wherein the processor executes the program to realize the steps in the method for determining the Fischer-Tropsch catalyst replacement strategy in the reactor in the running process. The device herein may be a server, PC, PAD, cell phone, etc.
The application also provides a computer program product adapted to perform, when executed on a data processing apparatus, a program initialising the method steps provided by any of the embodiments of the application for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor.
It will be appreciated by those skilled in the art that embodiments of the present application may be provided as a method, system, or computer program product. Accordingly, the present application may take the form of an entirely hardware embodiment, an entirely software embodiment or an embodiment combining software and hardware aspects. Furthermore, the present application may take the form of a computer program product embodied on one or more computer-usable storage media (including, but not limited to, disk storage, CD-ROM, optical storage, and the like) having computer-usable program code embodied therein.
The present application is described with reference to flowchart illustrations and/or block diagrams of methods, apparatus (systems) and computer program products according to embodiments of the application. It will be understood that each flow and/or block of the flowchart illustrations and/or block diagrams, and combinations of flows and/or blocks in the flowchart illustrations and/or block diagrams, can be implemented by computer program instructions. These computer program instructions may be provided to a processor of a general purpose computer, special purpose computer, embedded processor, or other programmable data processing apparatus to produce a machine, such that the instructions, which execute via the processor of the computer or other programmable data processing apparatus, create means for implementing the functions specified in the flowchart flow or flows and/or block diagram block or blocks.
These computer program instructions may also be stored in a computer-readable memory that can direct a computer or other programmable data processing apparatus to function in a particular manner, such that the instructions stored in the computer-readable memory produce an article of manufacture including instruction means which implement the function specified in the flowchart flow or flows and/or block diagram block or blocks.
These computer program instructions may also be loaded onto a computer or other programmable data processing apparatus to cause a series of operational steps to be performed on the computer or other programmable apparatus to produce a computer implemented process such that the instructions which execute on the computer or other programmable apparatus provide steps for implementing the functions specified in the flowchart flow or flows and/or block diagram block or blocks.
In one typical configuration, a computing device includes one or more processors (CPUs), input/output interfaces, network interfaces, and memory.
The memory may include volatile memory in a computer-readable medium, random Access Memory (RAM) and/or nonvolatile memory, etc., such as Read Only Memory (ROM) or flash RAM. Memory is an example of a computer-readable medium.
Computer readable media, including both non-transitory and non-transitory, removable and non-removable media, may implement information storage by any method or technology. The information may be computer readable instructions, data structures, modules of a program, or other data. Examples of storage media for a computer include, but are not limited to, phase change memory (PRAM), static Random Access Memory (SRAM), dynamic Random Access Memory (DRAM), other types of Random Access Memory (RAM), read Only Memory (ROM), electrically Erasable Programmable Read Only Memory (EEPROM), flash memory or other memory technology, compact disc read only memory (CD-ROM), digital Versatile Discs (DVD) or other optical storage, magnetic cassettes, magnetic tape magnetic disk storage or other magnetic storage devices, or any other non-transmission medium, which can be used to store information that can be accessed by a computing device. Computer-readable media, as defined herein, does not include transitory computer-readable media (transmission media), such as modulated data signals and carrier waves.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article or apparatus that comprises an element.
The foregoing is merely exemplary of the present application and is not intended to limit the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are to be included in the scope of the claims of the present application.
Claims (10)
1. A method for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor, the fischer-tropsch catalyst replacement strategy comprising a replacement interval and a replacement ratio for replacing a fischer-tropsch catalyst in the reactor, the method comprising:
acquiring an initial catalyst replacement interval and an initial catalyst replacement proportion;
determining a catalyst ratio corresponding to an operating duration based on a pre-established catalyst ratio distribution model, the initial catalyst replacement interval, and the initial catalyst replacement ratio;
determining the catalyst activity corresponding to the operation time based on a pre-established catalyst deactivation model;
determining a catalyst integrated activity corresponding to the operating duration based on the catalyst activity, the catalyst proportion, the initial catalyst replacement interval, and the initial catalyst replacement proportion;
Determining a loss ratio based on a pre-established loss model and the catalyst integrated activity; and
adjusting the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio to determine the replacement interval and the replacement ratio for replacing the Fischer-Tropsch catalyst in the reactor,
wherein the catalyst distribution ratio model is established by the following formula:
k·(1-k) n-i ，t-T-(i-1)·Δt，
wherein m is 0 And m h The mass of the catalyst is added in the start-up stage, h is the additive number in the start-up stage, M is the catalyst inventory, k is the replacement proportion, n is the total number of replacement, i is the replacement number, τ h Adding catalyst for start-up period, T is the operation time, T is the time for entering stable replacement period, deltat is the catalyst replacement interval,
the method further includes determining the catalyst integrated activity corresponding to the run length by the following formula:
wherein y represents the comprehensive activity of the catalyst, m 0 And m h The mass of the catalyst is added in the starting stage, p is the total number of times of the catalyst in the starting stage, h is the number of the catalyst in the starting stage, and M is the catalyst reservoirThe quantity k is the ratio of the substitutions, n is the total number of the substitutions, i is the number of the substitutions, τ h Adding catalyst at time interval of start-up, T is operation time, T is time of entering stable replacement stage, deltat is catalyst replacement interval, g (T) is catalyst activity,
The loss model is built by:
where n is the total number of permutations.
2. The method of claim 1, wherein said adjusting catalyst replacement intervals and catalyst replacement ratios according to said attrition ratio comprises:
obtaining a catalyst replacement interval limit value and a catalyst replacement proportion limit value;
selecting an adjusted catalyst replacement interval from a range of catalyst replacement intervals consisting of the catalyst replacement interval limit and the initial catalyst replacement interval; and
the adjusted catalyst replacement ratio is selected from a range of catalyst replacement ratios consisting of the catalyst replacement ratio limit and the initial catalyst replacement ratio.
3. The method of claim 1, wherein the catalyst activity comprises one or more of: conversion of CO, CO 2 Selectivity, CH 4 Selectivity and c3+ selectivity.
4. The method of claim 1, wherein the initial catalyst replacement interval and the initial catalyst replacement ratio are determined by a reduction time of a predetermined amount of catalyst,
wherein the initial catalyst replacement interval is a reduction time of the predetermined amount of catalyst; and
The initial catalyst replacement ratio is the ratio of the predetermined amount of catalyst to the total catalyst.
5. An apparatus for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor, the fischer-tropsch catalyst replacement strategy comprising a replacement interval and a replacement ratio for replacing a fischer-tropsch catalyst in the reactor, the apparatus comprising:
the acquisition module is used for acquiring an initial catalyst replacement interval and an initial catalyst replacement proportion;
the determining module is used for executing the following operations:
determining a catalyst ratio corresponding to an operating duration based on a pre-established catalyst ratio distribution model, the initial catalyst replacement interval, and the initial catalyst replacement ratio;
determining the catalyst activity corresponding to the operation time based on a pre-established catalyst deactivation model;
determining a catalyst integrated activity corresponding to the operating duration based on the catalyst activity, the catalyst proportion, the initial catalyst replacement interval, and the initial catalyst replacement proportion; and
Determining a loss ratio based on a pre-established loss model and the catalyst integrated activity,
wherein the catalyst distribution ratio model is established by the following formula:
k·(1-k) n-i ，t-T-(i-1)·Δt，
Wherein m is 0 And m h The mass of the catalyst is added in the start-up stage, h is the additive number in the start-up stage, M is the catalyst inventory, k is the replacement proportion, n is the total number of replacement, i is the replacement number, τ h To add to the start-up stageThe time interval of the catalyst, T is the operation duration, T is the time of entering the stable replacement stage, and Deltat is the catalyst replacement interval; and
an adjustment module for adjusting the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio to determine the replacement interval and the replacement ratio for replacing the Fischer-Tropsch catalyst in the reactor,
wherein the determination module further determines the catalyst integrated activity corresponding to the operating duration by the following formula:
wherein y represents the comprehensive activity of the catalyst, m 0 And m h The mass of the catalyst is added in the start-up stage, p is the total number of times of the catalyst in the start-up stage, h is the number of times of the catalyst in the start-up stage, M is the catalyst inventory, k is the replacement proportion, n is the total number of times of replacement, i is the replacement number, τ h Adding a catalyst for a time interval of a start-up stage, wherein T is an operation duration, T is a time of entering a stable replacement stage, deltat is a catalyst replacement interval, g (T) is a catalyst activity, and the loss model is established by the following steps:
Where n is the total number of permutations.
6. The apparatus of claim 5, wherein said adjusting catalyst replacement intervals and catalyst replacement ratios according to said attrition ratio in said adjustment module comprises:
obtaining a catalyst replacement interval limit value and a catalyst replacement proportion limit value;
selecting an adjusted catalyst replacement interval from a range of catalyst replacement intervals consisting of the catalyst replacement interval limit and the initial catalyst replacement interval; and
the adjusted catalyst replacement ratio is selected from a range of catalyst replacement ratios consisting of the catalyst replacement ratio limit and the initial catalyst replacement ratio.
7. The apparatus of claim 5, wherein the catalyst activity comprises one or more of: conversion of CO, CO 2 Selectivity, CH 4 Selectivity and c3+ selectivity.
8. The apparatus of claim 5, wherein the initial catalyst replacement interval and the initial catalyst replacement ratio in the acquisition module are determined by a reduction time of a predetermined amount of catalyst,
wherein the initial catalyst replacement interval is a reduction time of the predetermined amount of catalyst; and
The initial catalyst replacement ratio is the ratio of the predetermined amount of catalyst to the total catalyst.
9. A machine-readable storage medium having instructions stored thereon for causing a machine to perform the method for determining a fischer-tropsch catalyst replacement strategy in a runtime reactor of any of the preceding claims 1 to 4.
10. A processor for running a program, wherein the program is run for performing the method for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor according to any of the preceding claims 1 to 4.
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